JP2007514293A - System and method for forming a multi-component dielectric film - Google Patents

Abstract

A system and method for forming a dielectric film in a semiconductor application, and more particularly, a system and method for forming a multi-component dielectric film on a substrate using a mixed vaporized precursor.
The present invention provides a vaporized precursor mixture in which a mixture of vaporized precursors is present together in a chamber during a single pulse stage in an atomic layer deposition (ALD) process to form a multi-component film. Systems and methods for providing mixing are provided. The vaporized precursor consists of at least one different chemical component, and such different components will form a monolayer to form a multi-component film. In yet another aspect of the invention, a dielectric film having a composition gradient is provided.
[Selection] Figure 1

Description

CROSS-REFERENCE TO RELATED APPLICATIONS This application 2003 April 21 application entitled "method for producing a multi-component membrane" U.S. Provisional Patent Application Serial No. 60 / 464,458, November 17, 2003 filed US Provisional Application No. 60 / 520,964 entitled “ALD of HfSiON with Controlled Thickness and Composition Gradient” and “Atomic Layers of Metal or Mixed Metal Thin Films” filed Apr. 9, 2004 No. 60 / 560,952 of the provisional application entitled “Deposition” and claims the priority thereto, the entire disclosure of each of these patents being incorporated herein by reference. It is incorporated by.
In general, the present invention relates to systems and methods for forming dielectric films in semiconductor applications. More particularly, the present invention relates to a system and method for making a multi-component dielectric film on a substrate using a mixed vapor precursor.

  With the increasing sophistication and increasing momentum toward miniaturization of microelectronics, the number of transistors per integrated circuit is increasing exponentially, meeting the demand for faster, smaller and more powerful electronic systems. It is certain that it will increase even further. However, conventional silicon-based transistor geometries reach a critical point where the silicon dioxide gate dielectric is only a few atomic layers thick, leading to electron tunneling resulting in increased leakage current and power dissipation Will become more dominant. Therefore, an alternative dielectric that has a higher dielectric constant or dielectric constant than silicon dioxide and that can prevent current tunneling or leakage would be highly desirable. The most promising dielectric candidates to replace silicon dioxide include hafnium oxide, zirconium oxide, and tantalum oxide.

  Unfortunately, these materials are chemically and thermally unstable on silicon and, unlike silicon dioxide, form defects and charge traps at the interface between the metal dielectric and the silicon substrate. Charge traps and defects absorb the voltage applied to the gate and disrupt transistor performance and reliability. In order to limit the generation of interface charge traps and defects, a boundary layer of silicon dioxide is deposited between the dielectric and the silicon substrate. Although the silicon dioxide interface provides buffering from the dielectric to the silicon substrate, the silicon dioxide interface may not match the surface characteristics of the dielectric. Therefore, in order to fabricate ultra-thin high-k dielectrics, it is possible to improve the surface properties and chemical properties of the dielectric and silicon substrate, while at the same time requiring an interface that minimizes the equivalent physical oxide thickness. is there.

  Prior art deposition techniques for producing films such as chemical vapor deposition (CVD) have gradually been unable to cope with the requirements of advanced thin films. Although the CVD process can be tailored to provide a matching film with improved step coverage, the CVD process often requires high processing temperatures. For example, one of the obstacles to high-k gate dielectric fabrication is the formation of a boundary silicon oxide layer during the CVD process. A gas phase reaction in CVD causes particle generation. Another obstacle is the limitations of prior art CVD processes in the deposition of ultra thin films for high k gate dielectrics on silicon substrates.

An alternative to conventional CVD processes that deposit very thin films is atomic layer deposition (ALD). ALD has several advantages over conventional CVD. ALD can be performed at relatively low temperatures to match industry trends towards lower temperatures and can form matching thin film layers. An existing method of depositing a multi-component film such as an HfxSiyO ₂ (x + y = 1) film using ALD processing is to deposit a multilayer film of HfO ₂ and SiO ₂ films using a continuous vapor deposition method. is there. That is, the precursor chemicals are not mixed; instead, the Hf-containing precursor and the Si-containing precursor are independently and continuously introduced into the chamber in a pulsed manner to form a stack of HfO and SiO ₂ layers, respectively. Form. In fact, any mixing of the precursors is limited and one precursor is purged from the chamber before the second precursor is pulsed. With the laminate film formed to the desired thickness, the film is annealed to reach a more continuous composition throughout the film. This approach of accumulating layers of different stack films results in many electron traps in the film due to multiple interfaces, which requires high temperature thermal annealing to fix the traps. The addition of a high temperature thermal annealing step can increase the cost and time of manufacturing the semiconductor, and can also lead to undesirable external migration of elements from previously formed layers on the wafer. In addition, it is difficult to control the stoichiometric composition of the multi-component film in the laminate method. The dielectric constant (k), crystallization temperature, and refractive index of the HfSiOx film cannot be easily controlled by a conventional one-chemical continuous precursor pulse method (such as a laminate method). Furthermore, the cycle time required to form a film of the desired thickness using a conventional continuous pulse and purge of one chemical precursor at a time is impractical and is excessive for future IC manufacturing. It takes time.

  Attempts to make multi-component films using mixed precursors have been limited to conventional CVD methods. For example, US Pat. Nos. 6,537,613 and 6,238,734 (patents '613 and' 734), both granted to Senzaki et al., Generate compositional gradients containing metal and metalloid compounds by direct liquid injection. A system and method for doing so are generally disclosed. In direct liquid injection (DLI), the metal and metalloid precursors are mixed together to form a solvent-free liquid mixture prior to injection of the mixture into the deposition system.

However, the methods described in patents '613 and' 734 have some drawbacks associated with them. Specifically, it is the liquid mixture that is injected. Therefore, when the liquid mixture is not completely mixed, a film having a non-uniform composition and gradient is formed on the substrate. In addition, even when the correct volume of sample is supplied, there is no guarantee that the mixture will vaporize evenly because each precursor has a unique boiling point, vapor pressure, and volatility. Furthermore, when the difference in boiling point between the precursors is large, one precursor may decompose at the boiling point of the second to form fine particles or contaminants. In general, the precursors are not properly mixed resulting in a non-uniform film composition, or the mixing of the two vapors causes a pre-reaction in the gas phase to cause particles or contaminants to deposit on the wafer. Either resulting in formation.
Accordingly, there is a need for further development of a method for producing multi-component films. In particular, there is a need for a method of making a multi-component film using ALD processing. It is further desirable that the method provide easy control of the stoichiometric composition or gradient of the multi-component film.

U.S. Provisional Application No. 60 / 464,458 US Provisional Patent Application No. 60 / 520,964 US Provisional Patent Application No. 60 / 560,952 US Pat. No. 6,537,613 US Pat. No. 6,238,734 PCT patent application number PCT / US03 / 21575 PCT patent application number PCT / US03 / 22236

  In general, the inventor believes that a vaporized precursor mixture is present together in a chamber during a single pulse stage in an atomic layer deposition (ALD) process to form a multi-component film. I found a way to bring about the mixing of the body. The vaporized precursor consists of at least one different chemical component, and such different components will form a monolayer to form a multi-component film. The inventors refer to this method as “co-injection ALD”. Such a method is a departure from the prior art where vaporized precursors are pulsed separately into the chamber in an ALD process to form separate monolayers containing only one of the components.

  One aspect of the present invention provides a multi-component dielectric film by mixing vaporized precursors together and then injecting or co-injecting vaporized precursors such that the precursor mixture is present in the ALD chamber. Systems and methods for making are provided. The term “multicomponent” film as used herein means a film containing two or more metals or metalloid elements. Various multi-component films can be formed by the present invention including, but not limited to, metals, alloys, mixed metal oxides, silicates, nitrides, oxynitrides, and mixtures thereof.

  In one embodiment of the invention, two or more vaporized precursors, each containing at least one different chemical component, are transported together into a processing chamber to form a monolayer on the surface of the substrate, the monolayer being separated. There is provided a method of forming a thin film on the surface of a substrate by atomic layer deposition, characterized by containing each of the chemical components of: In general, the term co-implantation is used to mean that two or more precursors having at least one different chemical component are present in the chamber such that a film having a plurality of components is produced. . This can be accomplished by injecting or transporting the precursors together in the processing chamber either in the vapor state or in the liquid state (aerosol), or by mixing the precursors in the processing chamber. Mixing precursors prior to introduction into the processing chamber is preferred but not necessary.

  In another aspect, the present invention provides a system for forming a multi-component film. In one embodiment, the system generally includes one or more vaporizers, each coupled to a manifold. The manifold is configured to mix the vaporized precursor produced by the vaporizer. The manifold is also connected to the inlet to the reaction or deposition chamber, and the mixed precursor is injected into the chamber through the inlet. In one embodiment, the inlet comprises an injector such as a showerhead injector. It is also possible that the precursor can be mixed with an injector instead of a manifold.

  In yet another aspect of the invention, systems and methods are provided for forming multicomponent films having compositional gradients. In one embodiment, two or more vaporized precursors, each containing at least one different chemical component, are injected together into the processing chamber to form a monolayer on the surface of the substrate and injected into the chamber. A method of forming a multi-component film is provided, wherein the gas flow rate of each of the vaporization precursors is selectively controlled such that a desired composition gradient of one or more different chemical components is formed in the film. The

  In yet another aspect of the invention, a dielectric film having a composition gradient is provided that includes a silicon-rich lower layer, a nitrogen-rich upper layer, and at least one hafnium-rich layer between the upper and lower layers. In one embodiment, nitrogen is selectively deposited near or above the silicon substrate-dielectric interface to prevent boron diffusion. In yet another embodiment, boron diffusion is blocked without burdening the equivalent physical oxide thickness of the dielectric and the quality of the interface between the silicon and nitride dielectric, resulting in, for example, a higher trap density. It would be desirable to provide a system and method for this. In one embodiment, the composition gradient can be used to “buffer” the dielectric and the substrate. For example, when the substrate is silicon, the first layer is deposited with a smaller amount of the second deposited metal that is silicon rich and constitutes the dielectric. A second layer comprising primarily the deposited metal that constitutes the dielectric is deposited on top of the first layer in addition to a substantially smaller amount of silicon. In some embodiments, additional layers can be added to blend the surface properties and chemistry of adjacent layers. In various embodiments, each layer can be oxidized, reduced, nitrided, and combinations thereof in situ.

  Furthermore, the present invention provides a system and method for making a multi-component oxynitride film, wherein the multi-component film is formed by the method described above, and then the film comprises ozone, oxygen, peroxide, Oxidized at an elevated temperature using an oxidation reactant selected from the group consisting of water, air, nitrous oxide, nitric oxide, N-oxide, or mixtures thereof. Particularly advantageously, the oxidation step can be performed in situ. Following oxidation, the excited nitrogen source is continuously carried into the processing chamber and reacted with the oxide layer at an elevated temperature to form oxynitrides. Again, this step is performed in situ.

In a preferred embodiment, the present invention provides a system and method for making a multi-component oxynitride film by mixing a precursor containing a nitriding reactant into a chamber and performing an ALD process at a relatively low temperature. provide. Suitable nitriding agents are ammonia, deuterium substituted ammonia, ¹⁵ N-ammonia, amine or amide, hydrazine, alkyl hydrazine, nitrogen gas, nitric oxide, nitrous oxide, nitrogen radicals, N-oxide, or mixtures thereof. It can be selected from the group consisting of:
Other aspects, embodiments and advantages of the present invention will become apparent upon reading the following detailed description of the invention and the claims and referring to the drawings.

  Overall, the inventor presents a mixture of vaporized precursors in the chamber during a single pulse phase in an atomic layer deposition (ALD) process that forms a monolayer with multiple compounds on the surface of the substrate. We have discovered a method that results in mixing vaporized precursors. Vaporization precursors are composed of different chemical components, and such components will form a multi-component film. The inventors refer to this method as “co-injection ALD”. Such a method is a departure from the prior art where vaporized precursors are separately transported into the chamber or pulsed separately in the ALD process. Various multi-component films can be formed by the present invention including, but not limited to, metals, alloys, mixed metal oxides, silicates, nitrides, oxynitrides, and mixtures thereof.

In one aspect, the present invention provides a system and method for reproducibly and substantially equally controlling the stoichiometric composition of a multi-component film.
In a series of embodiments, the present invention provides systems and methods for making dielectrics that have a higher dielectric constant or dielectric constant than silicon dioxide and that can prevent current tunneling or leakage. . In another aspect, the present invention is a system and method for creating an interface that can improve the surface properties and chemistry of dielectric and silicon substrates while minimizing equivalent physical oxide thickness. I will provide a.

  Thus, in some embodiments and aspects of the present invention, the present invention is near or above the silicon substrate-dielectric interface to prevent boron diffusion and increase the crystallization temperature of the high-k layer. Systems and methods for selectively depositing nitrogen are provided. In yet another embodiment, boron diffusion is prevented without burdening the equivalent physical oxide thickness of the dielectric and the quality of the interface between the silicon and nitride dielectric, resulting in, for example, a higher trap density. It would be desirable to provide a system and method for this.

In an exemplary embodiment of the present invention, it is desirable to provide a system and method for performing low temperature nitridation of a film, and in another aspect of the invention, the invention provides a continuous nitrogen reactant in situ. Systems and methods are provided, eliminating the need for an external plasma source, and benefiting from fewer processing steps and shorter processing times.
In another aspect, the present invention provides a system for forming a multi-component film. In one embodiment, the system generally includes one or more vaporizers, each coupled to a manifold. The manifold is connected to an inlet to the reaction or deposition chamber, which consists of an injector such as a showerhead injector.

Each vaporizer contains a single deposition precursor that includes at least one deposited metal. Each vaporizer is connected to a mass flow controller and a temperature control unit. The mass flow controller and temperature unit can be selectively controlled to increase or decrease the concentration of deposition precursor present in the processing chamber. In one embodiment, each mass flow controller modifies the flow rate of the carrier gas through the system so that the carrier gas dilutes and transports the deposition precursor into the manifold or processing chamber.
In some series of embodiments, the vaporizer is a bubbler that vaporizes a single deposition precursor comprising at least one deposited metal. A pressurized gas containing a carrier gas is bubbled into the deposition precursor. The flow rate of the pressurized gas can be selectively controlled to adjust the concentration of deposition precursor present in the processing chamber.

In one embodiment, the manifold facilitates mixing of deposition precursors prior to delivery into the processing chamber. In some embodiments, the manifold includes a T-junction cavity that contains and mixes the deposition precursor prior to delivery into the processing chamber. The manifold can be heated to prevent condensation within the manifold, facilitating the flow of deposition precursor into the processing chamber.
The deposition precursor is typically supplied through a gas inlet, and a monolayer of deposition precursor is chemically and / or physically incorporated on the surface of the substrate. The substrate can be silicon, metal, alloy, glass, or a polymer, plastic, organic or inorganic processed product. The gas inlet can take a variety of forms. In one example, the gas inlet consists of one injector, a showerhead injector. Alternatively, the deposition precursor is supplied to the substrate surface by a plurality of injectors.

In general, when a single wafer chamber is used, the substrate is supported on a wafer carrier, called an electrostatic chuck or vacuum chuck, during deposition. In one embodiment, the chuck can cool or heat the substrate by conduction, convection, radiation, or non-radiation treatment, or a combination thereof. Alternatively, the wafer carrier can be a boat or cassette that supports multiple substrates for batch processing.
The inlet port switchably supplies an in-situ oxidation, reduction, or nitridation reactant into the processing chamber to facilitate continuous oxidation, reduction, or nitridation of the monolayer or substrate surface.

  In another aspect of the invention, a dielectric film having a composition gradient is provided that includes a silicon-rich lower layer, a nitrogen-rich upper layer, and at least one hafnium-rich layer between the upper and lower layers. In one embodiment, nitrogen is selectively deposited near or above the silicon substrate-dielectric interface to prevent boron diffusion. In yet another embodiment, boron diffusion is prevented without burdening the equivalent physical oxide thickness of the dielectric and the quality of the interface between the silicon and nitride dielectric, resulting in, for example, a higher trap density. It would be desirable to provide a system and method for this.

Furthermore, the present invention provides a system and method for making a multi-component oxynitride film, wherein the multi-component film is formed by the method described above, and then the film comprises ozone, oxygen, peroxide, water, air, nitrous oxide, nitric oxide, H ₂ O _2, N-oxides, or oxidized at high temperatures with an oxidizing reactant selected from the group consisting of mixtures thereof. Particularly advantageously, the oxidation can be carried out in situ. Following oxidation, an excited nitrogen source is continuously sent to the processing chamber where it can react with the oxide layer at high temperatures to form oxynitrides. Again, this step is performed in situ.

The present invention provides a system and method for making a multi-component oxynitride film by mixing a precursor containing a nitriding reactant into a chamber and performing an ALD process at a relatively low temperature. Suitable nitriding agents are ammonia, deuterium substituted ammonia, ¹⁵ N-ammonia, amine or amide, hydrazine, alkyl hydrazine, nitrogen gas, nitric oxide, nitrous oxide, nitrogen radicals, N-oxide, atomic nitrogen, or It can be selected from the group consisting of mixtures thereof.

  Particularly advantageously, the multi-component film of the present invention is formed with a composition gradient. The composition gradient can be used to “buffer” the dielectric and the substrate. For example, when the substrate is silicon, the first layer is deposited with a smaller amount of the second deposited metal that is silicon rich and constitutes the dielectric. A second layer mainly comprising the deposited metal that constitutes the dielectric is deposited on top of the first layer in addition to a substantially smaller amount of silicon. In some embodiments, additional layers can be added to blend the surface properties and chemistry of adjacent layers. In various embodiments, each layer can be oxidized, reduced, nitrided, and combinations thereof in situ. The composition gradient also provides a refractive index gradient within the film, which provides the unique optical properties of the film.

  FIG. 1 is a simplified conceptual diagram illustrating one embodiment of a system for making a multi-component film in accordance with one embodiment of the present invention. Referring generally to FIG. 1, the system 100 generally includes a processing chamber 102 that stores a wafer support 110 that supports a wafer 112 of a substrate. In order to supply deposition precursors and other gases 103 (e.g., a reactant gas such as an oxidizing gas or a diluent gas) into the chamber 102 to form various layers or films on the surface of the substrate. An inlet 114 is provided. In the exemplary embodiment, gas manifold 104 interconnects one or more vaporizers 107 and 109 to processing chamber 102. Although this exemplary embodiment shows two vaporizers, any number of vaporizers can be used. Each vaporizer includes a reservoir 116 and 118 and a vaporizer element 120 and 122 that hold a deposition precursor or a mixture of deposition precursors 124 and 126, respectively, to help vaporize the contents in the reservoirs 116 and 118. Gas flows through the element. The carrier gas flow into the vaporizer can be controlled using a mass flow controller (not shown) to control the flow rate and concentration of the vaporized deposition precursor. Optionally, each vaporizer can include a heating element (not shown) to facilitate vaporization of deposition precursors 124 and 126 held in reservoirs 116 and 118. Depending on the physical properties of the deposition precursors 124 and 126, a combination of carrier gas and heating may be required to vaporize the deposition precursors in the reservoirs 116 and 118.

In one embodiment of the present invention, a deposition precursor comprising at least one deposited metal is used, where the precursor has the chemical formula: M (L) _X , where M is Ti, Zr, Hf, Ta W, Mo, Ni, Si, Cr, Y, La, C, Nb, Zn, Fe, Cu, Al, Sn, Ce, Pr, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, Lu , Ga, In, Ru, Mn, Sr, Ba, Ca, V, Co, Os, Rh, Ir, Pd, Pt, Bi, Sn, Pb, Tl, Ge, or mixtures thereof A metal, L is an amine, amide, alkoxide, halogen, hydride, alkyl, azide, nitrate, nitrite, cyclopentaziniel, carbonyl, carboxylate, diketonate, alkene, alkyne, or substituted analogs thereof; as well as Of a ligand selected from the group consisting of the combination, x is a less than or equal integer valency against M.

It is advantageous to select the ligands (L) to be the same in each of the deposition precursors, and to avoid ligand exchange when each of the precursors is mixed in vapor form. Ligand exchange can result in the production of particulates, which can adversely affect the quality of the deposited film. Also suitable are ligands that do not undergo ligand exchange in vapor form.
In one preferred embodiment, two deposition precursors are selected, a first deposition precursor where M is hafnium and a second deposition precursor where M is silicon. Both the first and second deposition precursors have the same ligand (L) to avoid ligand exchange when the first and second deposition precursors are mixed. Suitable ligands include, but are not limited to, dimethylamine, diethylamine, diethylmethylamine, or tertiary butoxide.

  The hafnium source includes any one or combination of hafnium dialkylamide, hafnium alkoxide, hafnium diketonate, hafnium chloride (HfCl4), and tetrakis (ethylmethylamino) hafnium (TEMA-Hf). Can do. The silicon source includes at least one or a combination thereof such as aminosilane, silicon alkoxide, silicon dialkylamide, silane, silicon chloride, tetramethyldisiloxane (TMDSO), and tetrakis (ethylmethylamino) silicon (TEMA-Si). be able to. In one preferred embodiment, the liquid precursors 124 and 126 comprise TEMA-Hf and TEMASi, respectively.

  The deposition precursor is generally vaporized using a vaporizer. Each vaporizer contains only a single deposition precursor. Each vaporizer is connected to a mass flow controller and a heating mechanism. In accordance with one embodiment of the present invention, a composition gradient of one or more of the chemical components in the deposited film is provided as described above. In one example, selective control of composition is achieved by control of the amount of precursor vaporized. The amount of precursor vaporized is generally controlled by adjusting the gas flow controller and / or the temperature unit that heats the vaporizer to vaporize the desired concentration of the selected precursor. In addition or alternatively, a dilution gas can be conveyed into the injector 114 or manifold 104 (not shown) such that the flow rate of the dilution gas dilutes the amount of deposition precursor delivered to the chamber 102. It can be selectively controlled.

The vaporizer can comprise a bubbler that vaporizes a deposition precursor that includes at least one deposited metal. When the vaporizer is a bubbler, a pressurized gas, such as a carrier gas, is bubbled into the deposition precursor reservoirs 116 and 118. Useful carrier gases include nitrogen, argon, or helium gas. The pressurized gas dilutes the deposition precursor and feeds it into its respective deposition precursor conduits 106 and 108 to facilitate mixing of the deposition precursor. Optionally, to provide a compositional gradient in the film, the concentration of one or more deposition precursors can be controlled by changing the temperature of the bubbler, and the amount of deposition precursor vaporized selectively. Increased or decreased. Temperature control can be performed independently, or can be performed in conjunction with control of the mass flow controller and / or the flow rate of the carrier gas. Thus, each of the various control mechanisms can be used independently or in various combinations.
In other embodiments, due to the nature of the deposition precursor, the deposition precursor can be vaporized in the reservoirs 107 and 109 by photolysis or enzymatic or chemical catalysis.

  Referring again to FIG. 1, after the deposition precursors 124 and 126 are vaporized, the deposition precursors 124 and 126 are fed through the deposition precursor conduits 106 and 108 into the manifold 104. The deposition precursor conduits 106 and 108 may be any shape, size, and length. The conduits 106 and 108 can be made of metal, plastic, polymer, or alloy. In general, the conduit is made of the same material as the manifold 104. As with manifold 104, conduits 106 and 108 can be insulated or heated to facilitate vaporization. Optionally, conduits 106 and 108 and manifold 104 include a sampling region for measuring vapor concentration and vapor composition by spectroscopic analysis or spectrometry.

Mixing of the precursors can be facilitated by gravity or pressurized gas. Mixing can also be achieved by physical means of a plunger that forces the precursors 124 and 126 through the conduits 106 and 108 into the manifold 104, where the precursors 124 and 126 are mixed into a uniform deposition precursor. Can be. In some embodiments, conduits 124 and 126 merge and terminate at a T-junction 130 in manifold 104, and precursors 124 and 126 are mixed prior to delivery into processing chamber 102.
Alternatively, the conduits 106 and 108 can merge into a mixing region or cavity near the chamber 102, or an inlet to the chamber, and can carry their respective precursors directly. In some embodiments, a filter can be inserted or attached to the manifold 104 to isolate certain impurities or gases except those that are not desired.

Referring again to the manifold 104 and conduits 106 and 108, optionally, heating or cooling elements embedded inside or externally installed can be used, thereby adjusting the mixing and reducing particulates and impurities in the membrane. Generation is minimized.
The manifold 104 can take many forms suitable for precursor mixing prior to delivery of the precursor to the chamber 102. Manifold 104 may be a single conduit coupled to the vaporizer through a connection, such as a T-connection 130. Manifold 104 may include a cavity or reservoir that provides some residence time for mixing the precursors. In an alternative embodiment, the manifold can be completely removed and the deposition precursors are sent directly to the gas inlet 114 when they are transferred to the chamber 102 and mixed within the gas inlet 114 (e.g., The gas inlet consists of an injector).

  Still referring to FIG. 1, with precursors 124 and 126 vaporized, deposition precursors 124 and 126 are delivered to chamber 102 through one or more gas inlets 114. The gas inlet can take various forms for the supply of gas to the chamber. In one embodiment, the gas inlet comprises an injector such as a showerhead. Although the exemplary embodiment shows a single wafer chamber with one gas inlet 114, the present invention can be used with a batch processing chamber or with a mini-batch chamber. In batch or mini-batch chambers, multiple gas inlets are used, and gas is generally carried in a parallel flow or cross flow manner over each substrate. An example of a mini-batch chamber is described in PCT Patent Application No. PCT / US03 / 21575, entitled “Heat Treatment System and Configurable Vertical Chamber”, the disclosure of which is incorporated herein by reference.

  A layer of a deposition mixture including precursors 124 and 126 is deposited on the substrate 112. Suitable substrates include metal, alloy, glass, polymer, plastic, organic, or inorganic processed products. Depending on the mode of deposition, one or more monolayers of the deposition mixture will be formed on the substrate 112. A preferred deposition method is atomic layer deposition. However, the system and method of the present invention is amenable to other deposition techniques such as “chemical vapor deposition”. It is also within the scope of the present invention to incorporate a showerhead using a plurality of adjustable injectors in the processing chamber 102 to provide the desired membrane.

  Referring again to FIG. 1, following deposition of the deposition mixture, the excess mixture is connected to a vacuum pump that controls the system pressure and gas flow to ensure a rapid purge of the processing chamber 102 after each deposition process. Removed from the system. Wafer carrier 110 is used to support and heat the substrate during the deposition or annealing step. A wafer carrier generally includes heating and cooling elements formed therein. An external heater (not shown) can also be used to control the temperature of the processing chamber. Preferably, the wafer carrier 110 is a vacuum chuck or an electrostatic chuck.

  The processing chamber 102 has an inlet 103 that can be switched to continuously supply other gases used for processing and cleaning in the chamber. Reactant gas is conveyed to the chamber through inlet 103. Suitable reactant gases include oxidizing gas, reducing gas, nitriding gas, or mixtures thereof. Other gases that may be sent through the inlet 103 include carrier gas or inert gas, or mixtures thereof.

  In one preferred embodiment, the vaporized deposition precursor is mixed in the manifold prior to introduction into the reaction chamber to provide a more uniform film and allow maximum control of the film composition. The However, it is also possible to send each precursor separately to a gas inlet, such as an injector, which mixes them as the gas is injected into the chamber, thus eliminating the need for a separate manifold. In view of the teachings of the present invention, various mechanical embodiments are suitable, and the present invention is not limited to any one mechanical configuration. The teachings of the present invention teach at least some mixing of various different precursors such that a mixture of precursors having different chemical components is present in the reaction chamber to form a film having multiple components within a single layer. Provides that happens.

Reactant gas is introduced into the processing chamber 102 through the inlet 103 to process and / or react with the monolayer containing the deposition mixture on the surface of the substrate 112. The reactant gas can be mixed with the deposition precursor in the gas inlet 114 or fed directly into the processing chamber 102 in sequence or simultaneously.
Various reactant gases can be used depending on the application. When the reactant gas is an oxidizing gas, the monolayer is oxidized. When the reactant gas is reduced, the monolayer is reduced. Similarly, when the reactant gas is a nitriding gas, the single layer is nitrided. Suitable oxidizing gases include ozone, oxygen, singlet oxygen, triplet oxygen, water, peroxide, air, nitrous oxide, nitric oxide, H ₂ O ₂ , and mixtures thereof. Suitable reducing gases include hydrogen. Suitable nitriding gases include ammonia, deuterium substituted ammonia, ¹⁵ N-ammonia, hydrazine, alkyl hydrazine, nitrogen dioxide, nitrous oxide, nitrogen radical, nitric oxide, N-oxide, amide, amine, or mixtures thereof There is. In another embodiment, after the deposition precursor has been deposited on the substrate 112, the substrate 112 is transferred in a vacuum to a second processing apparatus that can nitride, oxidize, reduce, or anneal a single layer of the substrate 112. be able to.

In one example, deposition precursors TEMA-Hf and TEMA-Si are vaporized to form a multi-component film comprising HfSiN by ALD, then mixed together and transported to a processing chamber (also referred to as “pulsed”) ), A nitrogen-containing source such as ammonia is added to form HfSiN.
In one example, the ALD process is performed in the range of about 25 to 800 ° C, more usually in the range of about 50 to 600 ° C, and most usually in the range of about 100 to 500 ° C. The pressure in the processing chamber is in the range of about 0.001 mTorr to 600 Torr, more usually in the range of about 0.01 mTorr to 100 Torr, and most typically in the range of about 0.1 mTorr to 10 Torr. This pressure range extends to both the pulse and purge phases. The overall inert gas flow rate is typically in the range of about 0 to 20,000 sccm, including the carrier gas in the bubbler when a bubbler is used, and more usually in the range of about 0 to 5,000 sccm. is there.
Optionally, after the deposition precursor has been deposited on the substrate 112, the substrate 112 can be transferred in a vacuum to a second processing apparatus that can nitride, oxidize, reduce, or anneal a single layer of the substrate 112. it can.

  FIG. 2 is a cross-sectional view of the multilayer gate dielectric of the present invention. The first layer 200 is selected to promote the desirable properties of high mobility (higher transistor speed) and stable interface to the substrate 112. Suitably the first layer is a metal silicate or oxide having a high dielectric constant. Preferably, the first layer is a silicon rich metal silicate. The silicon component in the first layer metal silicate reduces the formation of interface defects by mitigating the incompatibility between the pure metal or metal oxide and the interface silicon dioxide residue on the substrate 112. Let The metal component in the metal silicate helps to improve the dielectric properties of the first layer. Suitable metals, alloys, or mixed metal oxides, nitrides, silicates, or oxynitrides of the present invention include, but are not limited to, Ti, Zr, Hf, Ta, W, Mo, Ni, Si , Cr, Y, La, C, Nb, Zn, Fe, Cu, Al, Sn, Ce, Pr, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ga, In, Ru, Mn , Sr, Ba, Ca, V, Co, Os, Rh, Ir, Pd, Pt, Bi, Sn, Pb, Tl, Ge, or mixtures thereof.

  One embodiment of the present invention is illustrated in the flow diagram of FIG. This example is shown for illustrative purposes only and is not meant to limit the invention in any way. In an exemplary embodiment, a first precursor vaporizer is provided having a first precursor comprising Hf (stage 150). A second precursor vaporizer having a second precursor comprising Si is also provided (stage 152). A substrate or wafer is placed on a chuck in the reaction chamber (step 154), the processing chamber is evacuated (step 156), and the substrate is heated to a predetermined processing temperature (step 158). As mentioned above, the processing temperature is preferably about 50 to 800 ° C, more preferably about 100 to 500 ° C. The first and second precursors are vaporized by bubbling the gas through the reservoir to form first and second vaporized precursors (stage 160), mixed (stage 162), and flow into the reaction chamber. (164). The mixed first and second vaporized precursors are guided onto the substrate through a gas inlet called a showerhead or an injection nozzle (166).

  The present invention further provides a multi-component film or layer having a composition gradient as shown in FIG. With reference to FIGS. 1 and 2, the deposition of the first layer 200 on the silicon substrate 112 is performed in the processing chamber 102. In one example, a film of HfSiO is formed, hafnium is vaporized in the vaporizer 107 and silicon is vaporized in the vaporizer 109. Hafnium and silicon deposition precursor vapors are flowed into the manifold 104 by a carrier gas. Inside the manifold, the deposition precursor mixes and is fed to the gas inlet 114 as a deposition mixture. The gas inlet 114 delivers the deposition mixture to the processing chamber 102, which contacts the surface of the substrate 112 and is captured on the surface to form a monolayer of the deposition mixture on the substrate 112. After the processing chamber 112 is purged with an inert gas or evacuated under vacuum, ozone gas is continuously pulsed into the processing chamber 102 through the inlet 103. The reactant gas saturates the monolayer on the substrate 112 to form an atomic layer containing hafnium, silicon, and oxygen, where the silicon content is higher than hafnium.

FIG. 4 shows that by changing the flow rate of the deposition precursors 124 and 126, the concentration of silicon relative to hafnium can be adjusted to provide a multi-component film. 5, changes in the silicon or hafnium concentration, indicating that it is governed in most cases by the formula Hf _x Si _1-x O ₂ in the case of x = 0-1.
XPS studies on Hf _x Si _1-x O ₂ films helped to elucidate the bonding arrangement of atoms in the film. FIG. 6a represents the XPS spectrum of hafnium in the film. Based on the strength of the absorption band and the magnitude of the binding energy, hafnium is found mostly in the form of silicates. Very few impurities such as HfO ₂ are observed in the spectrum. Referring now to FIG. 6b, the XPS spectrum of silicon reveals that silicon is also mostly present as silicate, with little or no formation of SiO ₂ . The XPS results clarify the advantages of the present invention. That is, the formation of a uniform hafnium silicate film with little or no HfO ₂ or SiO ₂ patches.

Referring now to FIG. 7, the refractive index of the dielectric film of the present invention decreases with increasing silicon content. FIG. 7 shows that heating the film at 900 ° C. in an N ₂ atmosphere does not cause thermal denaturation.
FIG. 8 shows that the deposition rate is temperature dependent. The linear growth rate of Hf _x Si _1-x O ₂ increases with temperature. However, above 400 ° C., the deposition rate is substantially increased because the atomic layer deposition (ALD) process uses a chemical vapor deposition (CVD) mechanism. “Transmission electron microscope (TEM)” cross-sectional images of Hf _x Si _1-x O ₂ films deposited at 400 ° C. on HF last silicon substrates at various thicknesses show a similar boundary layer thickness measured at about 1 nm. Show. Comparing FIGS. 9a, 9b, and 9c, each has a dielectric thickness of 2.3 nm, 4.3 nm, and 6.5 nm, respectively, but the interface thickness is independent of the dielectric thickness. . This suggests that when ozone is used as an oxidation reactant in the ALD process, interface oxidation may occur during the initial film fabrication.

Heating at a high temperature does not change the amorphous state of the dielectric, but the annealing process reduces the interface oxide layer. FIG. 10 shows a TEM image of the annealed Hf _x Si _1-x O ₂ film. Comparing the thickness of the interface oxide layer with FIG. 9, the annealing treatment appears to reduce the interface layer by 0.3 nm and does not change either the capacitance-voltage (CV) or current-voltage (IV) relationship. FIG. 11 shows that the film is electrically stable to annealing. Neither the capacitance equivalent thickness (CET) nor the low leakage current density was significantly affected by the annealing step.

Stress hysteresis measurements for a 50 nm thick Hf _0.34 Si _0.66 O ₂ film during annealing up to 900 ° C. were monitored. As can be seen in FIG. 12, the constant slope during the temperature rise shows a fairly stable difference in thermal expansion between the deposited Hf _0.34 Si _0.66 O ₂ film and the silicon substrate. At about 700 ° C., the stress becomes more tensile, indicating a morphological change in the microcrystalline state. Compared to the HfO ₂ film having an increase in stress at about 450 ° C. (not shown) deposited by ALD from TEMAHf and O ₃ at 300 ° C., the increase in film stress transition temperature in Hf _x Si _1-x O ₂ is This is due to the increase in silicon content. Thus, increasing the silicon content increases the temperature at which the film crystallizes.

Suitable sources of hafnium include hafnium dialkylamide, hafnium alkoxide, hafnium diketonate, or hafnium halide. Suitable sources of silicon include silicon halides, silicon dialkylamides or amines, silicon alkoxides, silanes, disilanes, siloxanes, aminodisilanes, and disilicon halides. In general, the hafnium and silicon sources are selected to have a common ligand, avoiding the troublesome problems arising from ligand exchange. Covalently cross-linked mixed metals as disclosed in PCT Patent Application No. PCT / US03 / 22236, entitled “Molecular Layer Deposition of Thin Films with Mixed Components”, incorporated herein by reference. As well as non-covalently bonded mixed metals can be used as precursors for deposition. Non-covalent bond modes include hydrogen bond, coordination bond, metal-metal bond, metal-π, metal-π ^* , π-π bond, sigma-sigma bond, ionic bond, van der Waals interaction , Hydrophobic / hydrophilic interactions, polar bonds, or dipole moment interactions. Inert gas sources include carrier gases such as argon, nitrogen, inert gases, or mixtures thereof.

  Referring again to FIG. 2, a second layer 202 is deposited on the first layer 200, and the second layer 202 has a higher hafnium concentration than silicon, ie, hafnium> silicon. A higher concentration of hafnium ensures that the overall configuration of the dielectric behaves like a high-k hafnium dielectric. The presence of silicon in the second layer 202 is a gradual change from the first layer 200 so that there are no abrupt compositional interfaces that can cause electrical leakage or defects between the individual layers. A stoichiometric transition. Subsequent oxidation with ozone provides the second layer 202.

In various embodiments of the present invention, the third layer 203 is optionally deposited on the second layer 202 such that it mainly comprises hafnium, ie, hafnium >> silicon, and has a composition gradient. A stack of dielectric layers can be formed. Oxidation using oxidation reactants mainly produces hafnium dioxide. Using this technique, films with uniform gradients, thicknesses, and compositions can be produced with precision and control.
In another aspect, the third layer 203 can be nitrided using a nitridation reactant. Inclusion of nitrogen prevents the diffusion of impurities such as boron through the dielectric and increases the long-term performance and reliability of the film.

  In some embodiments, the third layer 203 can be thermally nitrided in the presence of ammonia gas during the post-deposition annealing step. In contrast, in other embodiments, the third layer 203 can be nitrided using high energy nitrogen particles generated away from the processing chamber 102. An XPS spectrum of an exemplary annealed film using ammonia according to one embodiment of the present invention is shown in FIG. Again, compared to the HfSiO reference shown in FIG. 13, the presence of a nitrogen peak near 400 eV indicates the incorporation of nitrogen into the HfSiO layer. Measurements at various take-off angles (TOA) detect the presence of nitrogen not only on the dielectric surface but also deep inside the film.

  Optionally, instead of relying on heating to form and anneal the nitride layer, if desired, nitriding is promoted by light or any combination of light, heating, and chemical initiators. be able to. For example, in certain embodiments, direct plasma, remote plasma, downstream plasma, ultraviolet photon energy, or a combination thereof can be used to promote nitridation. Activation energy sources include plasma, light, laser, radical, and microwave energy sources, and mixtures thereof.

In another embodiment, as described above, suitable nitrogen sources include ammonia, deuterium substituted ammonia, ¹⁵ N enriched ammonia, amine, amide, nitrogen gas, hydrazine, alkyl hydrazine, nitrous oxide, monoxide. There are nitrogen, nitrogen radicals, N-oxides, or mixtures thereof.
In yet another aspect of the invention, relating to nitridation of a film, an environmental method of nitriding a dielectric is provided. FIG. 14 shows that the rate of HfO ₂ deposition resulting from the reaction between the hafnium dialkylamide precursor and ozone unexpectedly increases with decreasing reaction temperature. Due to the reactivity of ozone to hafnium dialkylamide, HfSiOx 300 was deposited on substrate precursor 112 as shown in FIG. 14 by vaporizing hafnium and silicon in vaporizers 107 and 109 of FIG. 1, respectively. . Ozone is supplied through the inlet 103 into the processing chamber 102 containing the substrate 112. Oxidation occurs rapidly at relatively low temperatures, such as at 16a, resulting in hafnium oxide 302. The oxynitride layer 304 is preferably on the metal oxide 302 to protect the layer 302 from boron diffusion from the gate electrode.
There are two ways to deposit the oxynitride layer 304. In the first method, as shown in FIG. 16 a, deposition precursors 124 and 126 are vaporized and injected into the processing chamber 102 to form a monolayer of deposition mixture on the substrate 112.

  Referring now to FIG. 16a, a subsequent thermal oxynitridation anneal at 800 ° C. with ammonia is acceptable, despite the low temperature that produces oxide 302, but is not preferred from a processing standpoint. Is. Structurally, such a high annealing temperature raises great concerns. That is, the crystallization of the oxide layer 302 poses the possibility of intrinsic defects deep inside the oxide 302 or at its grain boundaries.

In a preferred embodiment of the present invention, a second method of depositing oxynitride is shown in FIG. 16b. The method in FIG. 16b is a more economical route to oxynitride 304 compared to the method in FIG. 16a. Since ozone reacts readily with the metal dialkylamides, the deposition mixture is first deposited on the substrate 112 and in turn treated with ammonia in situ. Following the formation of nitride 303 at a relatively low temperature, oxidation with ozone proceeds to complete the reaction, producing oxynitride 304.
In some embodiments of the invention, deuterium substituted ammonia or ¹⁵ N-ammonia is preferred.
FIG. 17 shows a composition profile below the surface of oxynitride 304. The nitrogen concentration is maximal on the surface of the film, but gradually decreases below the surface until it reaches the surface of HfO ₂ . When the film further enters the film, the concentration of HfO ₂ 302 is lowered until the boundary layer of the silicon substrate 112 is reached, and is taken over by HfSiO _x 300.

According to the present invention, many layers of HfSiON having different film thicknesses and nitrogen or oxygen concentrations can be deposited. Although specific examples illustrating the formation of SiO ₂ , HfO ₂ , HfSiO _x , HfN, SiN, SiON, and HfSiON are set forth herein, the method and ALD system of the present invention is not limited to metals, alloys. It will be apparent to those skilled in the art that it can be used to produce thin films of any thickness, composition, or type, including mixed metal oxides, silicates, nitrides, oxynitrides, or mixtures thereof. I will.
The foregoing descriptions of specific embodiments of the present invention have been presented for purposes of illustration and description. They are not intended to be exhaustive or to limit the invention to the precise form disclosed, and obviously many modifications, embodiments, and variations are possible in light of the above teachings. . It is intended that the scope of the invention be defined by the claims appended hereto and their equivalents.

1 is a schematic block diagram of a system for producing a multi-component multilayer film according to an embodiment of the present invention. 1 is a cross-sectional view of a high-k dielectric gate material formed using the system and method of the present invention. 3 is a flow diagram illustrating a method of making a composition gradient film according to an embodiment of the invention. 6 is a graph showing the relationship between film composition and deposition precursor gas flow, showing a specific example where the deposition and composition of the hafnium-silicon film can be changed by controlling the hafnium and silicon deposition gas flow rates. 4 is a table showing the results of atomic composition analysis of various HfSiO films produced by the system and method of the present invention. This result shows that the ratio of oxygen atoms to hafnium and silicon atoms is about 2 over a given hafnium and silicon content concentration. These results, HfSiO film produced by the system and method of the present invention, over a particular range indicates that to provide a membrane having a structural formula _{Hf x Si 1-x O 2} . The percentage ratio of carbon, hydrogen, and nitrogen is only found in trace amounts. The “X” spectrum of the film having the chemical formula Hf _0.5 Si _0.5 O ₂ produced by the system and method of the present invention highlights the XPS spectrum of the 4f region of hafnium found in the film and shows little or no impurities in the spectrum. 2 is a graph showing a “Linear Photoelectron Spectroscopy (XPS)” spectrum. “X” of a film having the chemical formula Hf _0.5 Si _0.5 O ₂ produced by the system and method of the present invention highlighting the XPS spectrum of the 2p region of silicon found in the film and showing little or no impurities in the spectrum. 2 is a graph showing a “Linear Photoelectron Spectroscopy (XPS)” spectrum. Is a graph comparing the refractive index regarding deposited upon the film and annealed films after deposition, to a Hf / (Hf + Si) 50nm thickness varying Hf _x Si _1-x O ₂ film on the silicon wafer was measured as a function of the ratio It is a figure showing a refractive index. Hafnium with ozone - shows respect Hf _x Si _1-x O ₂ film deposition temperature changes in the deposition rate for obtained by oxidation of the silicon film. Shows a TEM image of 2.3nm dielectric Hf _0.58 Si _0.42 O ₂ film having a thickness, the thickness of the boundary surface is measured to be about 1 nm, Hf _0.58 Si deposited at 400 ° C. on a silicon substrate HF last treatment it is a view showing a TEM cross-sectional image of _0.42 O ₂ film. 4 shows a TEM image of a Hf _0.58 Si _0.42 O ₂ film having a dielectric thickness of 4.3 nm and a Hf _0.58 Si deposited at 400 ° C. on a HF-last-treated silicon substrate having a boundary thickness of about 1 nm. it is a view showing a TEM cross-sectional image of _0.42 O ₂ film. 6 shows a TEM image of a Hf _0.58 Si _0.42 O ₂ film having a dielectric thickness of 6.5 nm and a Hf _0.58 Si deposited at 400 ° C. on a HF- lasted silicon substrate having a boundary thickness of about 1 nm. it is a view showing a TEM cross-sectional image of _0.42 O ₂ film. FIG. 6 is a cross-sectional TEM image of Hf _0.58 Si _0.42 O ₂ having a polysilicon cap layer after annealing at 700 ° C. in N ₂ . For various Hf _x Si _1-x O ₂ film on the silicon wafer was HF last treatment is a diagram obtained by measuring the capacitance equivalent thickness (CET) and leakage current density as a function of Hf content. About 50nm thick Hf _0.34 Si _0.66 O ₂ film, a diagram obtained by measuring the film tensile stress as a function of temperature. The XPS spectrum of the HfSiON film at various take-off angles (TOA) compared to HfSiO reveals the presence of nitrogen in the film, and the nitrogen 1s for the HfSiO film nitrided with ammonia in the post-deposition annealing stage FIG. 6 shows an “X-ray photoelectron spectroscopy (XPS)” spectrum for the hafnium 4p _3/2 region. It is a graph of the deposition rate as a function of the deposition temperature of HfO ₂ produced by oxidation of hafnium dialkylamide with ozone. FIG. 3 is a cross-sectional view of a thin film having a composition gradient formed by the co-implantation system and method of the present invention, showing the thin film continuously formed in situ, including layers of HfSiOx, HfO2, and HfOxNy or HfSiON. Reaction scheme illustrating two different methods of producing the metal, alloy, or mixed metal oxynitrides of the present invention, showing relatively high temperature processing to produce oxynitrides, wherein the oxidation stage precedes the nitridation stage FIG. FIG. 2 shows a reaction scheme illustrating two different methods of producing the metal, alloy, or mixed metal oxynitrides of the present invention, where the oxidation stage waits until the film is nitrided under a relatively low temperature. . The nitrogen concentration is maximum on the surface of the film and gradually decreases below the surface until it reaches the HfO ₂ layer, and when further entering the film, the concentration of HfO ₂ decreases until it reaches the boundary layer of the silicon substrate. FIG. 2 shows a composition profile below the surface of a typical oxynitride film inherited by HfSiO _x .

Explanation of symbols

100 system 102 processing chamber 104 gas manifold 107, 109 vaporizer 112 wafer 114 gas inlet 124, 126 deposition precursor or mixture of deposition precursors

Claims (25)

A method of forming a film on a surface of a substrate,
Two or more precursors, each containing at least one different chemical component, are transported together into a processing chamber to form a monolayer on the surface of the substrate;
The monolayer contains each of the separate chemical components;
A method characterized by that. A method of forming a film on a surface of a substrate,
Two or more precursors, each containing at least one different chemical component, are transported together into a processing chamber to form a monolayer on the surface of the substrate;
The amount of each of the precursors delivered to the processing chamber is selectively controlled such that one or more desired composition gradients of the chemical components are formed in the film.
A method characterized by that. The precursor has the chemical formula:
M (L) x
Where M is Ti, Zr, Hf, Ta, W, Mo, Ni, Si, Cr, Y, La, C, Nb, Zn, Fe, Cu, Al, Sn, Ce, Pr, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ga, In, Ru, Mn, Sr, Ba, Ca, V, Co, Os, Rh, Ir, Pd, Pt, Bi, Sn, A metal selected from the group of Pb, Tl, Ge, or mixtures thereof, wherein L is an amine, amide, alkoxide, halogen, hydride, alkyl, azide, nitrate, nitrite, cyclopentadiniel, carbonyl, A ligand selected from the group consisting of carboxylate, diketonate, alkene, alkyne, or substituted analogs thereof, and combinations thereof, wherein x is an integer equal to or less than the valence for M Ah The method of claim 1 or claim 2, characterized in that.   3. The method of claim 1 or claim 2, further comprising providing at least one reactant that reacts with the monolayer.   The method of claim 4, wherein the at least one reactant is fed subsequent to or simultaneously with the precursor.   The method of claim 4, wherein the at least one reactant is a nitriding reactant, a reducing reactant, an oxidizing reactant, or a mixture thereof.   The nitriding reactant is composed of ammonia, deuterium-substituted ammonia, 15N-ammonia, amine or amide, hydrazine, alkyl hydrazine, nitrogen gas, nitric oxide, nitrous oxide, nitrogen radical, N-oxide, or a mixture thereof. The method of claim 6, wherein the method is selected from a group. The oxidation reactant is a group consisting of ozone, oxygen, singlet oxygen, triplet oxygen, atomic oxygen, water, peroxide, air, nitrous oxide, nitric oxide, H ₂ O ₂ , and mixtures thereof. The method of claim 6, wherein the method is selected from: A method of forming a multi-component film on a surface of a substrate,
Vaporizing two or more precursors each containing at least one different chemical component;
Conveying the two or more precursors into a processing chamber so that the precursors are present together in the processing chamber;
Forming a monolayer on the surface of the substrate containing each of the separate chemical components;
Purging the processing chamber;
A method comprising the steps of:   The method of claim 9, wherein the forming is performed at a temperature in the range of about 20 to 800 degrees Celsius.   The method of claim 1, wherein the processing chamber is at a pressure in the range of about 0.001 mTorr to 600 Torr.   10. The substrate according to claim 1, wherein the substrate surface is selected from the group consisting of silicon, plastic, polymer, metal, alloy, organic substance, inorganic substance, or a mixture thereof. 2. The method according to item 1.   The method of claim 9, wherein the step of conveying further comprises the step of mixing the two or more precursors to convey the mixture of precursors into the processing chamber.   The method of claim 9, wherein the purging further comprises introducing a carrier gas and discharging the precursor from the chamber.   The method of claim 9, further comprising transporting a reactant gas in contact with the monolayer formed on the surface of the substrate to the processing chamber.   14. The method of claim 13, wherein the gas flow rate to the processing chamber is in the range of about 0 to 20,000 sccm. A dielectric film having a composition gradient,
A silicon-rich underlayer,
A nitrogen-rich upper layer,
A hafnium-rich layer formed between the upper and lower layers;
A film characterized by containing.   18. The dielectric film according to claim 17, wherein each of the silicon-rich lower layer, the hafnium intermediate layer, and the nitrogen-rich upper layer includes at least one common composition element.   The dielectric film according to claim 18, wherein the at least one common composition element is selected from the group consisting of oxygen, nitrogen, and metal.   The metals are Ti, Zr, Hf, Ta, W, Mo, Ni, Si, Cr, Y, La, C, Nb, Zn, Fe, Cu, Al, Sn, Ce, Pr, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ga, In, Ru, Mn, Sr, Ba, Ca, V, Co, Os, Rh, Ir, Pd, Pt, Bi, Sn, Pb, Tl, Ge, 20. The dielectric film according to claim 19, wherein the dielectric film is selected from the group consisting of: and a mixture thereof.   The dielectric film according to claim 19, wherein the metal further includes a metal, an alloy, or a mixed metal oxide, silicate, nitride, oxynitride, or a mixture thereof. A system for atomic layer deposition,
At least a first vaporizer containing a first deposition precursor for deposition;
At least a second vaporizer containing a second deposition precursor for deposition;
A processing chamber adapted to perform an atomic layer deposition process;
A manifold coupled to the first and second vaporizers and the processing chamber, wherein the manifold is adapted to mix and transport the first and second deposition precursors to the processing chamber;
A system characterized by including. The processing chamber comprises
A gas inlet connected to the manifold;
An inlet for supplying at least one reactant gas, wherein the at least one reactant is supplied in situ in the processing chamber continuously or simultaneously;
The system of claim 22 further comprising:   The monolayer is selected from the group consisting of one or more metals, alloys, or mixed metal oxides, silicates, nitrides, and oxynitrides. Or the method according to claim 9.   10. Each of the single layers is compositionally variable, and is electrically and physically compatible with the adjacent single layer. The method described in 1.

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